Triols by hydrogenation of bicyclic furodioxoles

ABSTRACT

Triols having a neopentyl structure are prepared by catalytic hydrogenation, preferably in the presence of water, of certain bicyclic furodioxole compounds at elevated temperatures and pressures. For example, 3,3-dimethyl-1,2,4-butanetriol is prepared by catalytic hydrogenation of tetrahydro-( 2,3-d) -1,3dioxol-5-ol at temperatures in the range from about 75*C. to about 175* C. and pressures of about 100 psi to about 10,000 psi. Triols are useful solvents and intermediates in the preparation of alkyd coating compositions and plasticizers for resinous materials such as polyvinyl chloride.

ilnited States Patent n 1 Robinson et a1.

[ 1 Sept. 18, 1973 I TRIOLS BY HYDROGENATION OF BICYCLIC FURODIOXOLES [75] Inventors: Alfred G. Robinson; Alden E. Blood;

Hugh J. Hagemeyer, Jr., all of Longview, Tex.

[73] Assignee: Eastman Kodak Company,

Rochester, NY.

[22] Filed: Apr. 14, 1969 [21] Appl. No.: 816,073

Related U.S. Application Data [63] Continuation-impart of Ser. No. 798,803, Feb. 12,

1969, Pat. No. 3,564,017.

[52] U.S. Cl. 260/635 E, 252/194, 252/364,

260/75 R, 260/92.8 R, 260/635 R [51] Int. Cl C03c 31/18, C08f 3/30, C08g 17/00 [58] Field of Search 260/635 R, 635 E [56] References Cited UNITED STATES PATENTS 2,174,651 10/1939 Byrkit 260/635 C 2,898,492 5/1959 Fischer et a1 260/635 E 3,168,534 2/1965 Payne 260/635 E 2,440,929 5/1948 Bremner et a1. 260/635 E FOREIGN PATENTS OR APPLICATIONS 527,170 7/1956 Canada 260/635 E OTHER PUBLICATIONS Broquet et al., Chem. Abstracts, Vol. 67, (1967), page 7,724, item 82010Y.

Primary Examiner-Leon Zitver Assistant ExaminerJoseph E. Evans Attorney-Cecil D. Quillen, Jr. and John A. Gazewood [57] ABSTRACT 28 Claims, No Drawings TRIOLS BY HYDROGENATTON OF BICYCLIC FURODIOXOLES RELATED APPLICATIONS This application is a continuation-in-part of copending application Ser. No. 798,803 filed Feb. 12, 1969, now US. Pat. No. 3,564,017.

This invention relates to novel polyhydroxy compounds and to their preparation. More particularly, the invention is concerned with novel organic triols having the neopentyl structure and to methods for their preparation.

The novel triols of the present invention can be regarded generically as 3,3-dialkyI-l,2,4-butanetriols. The invention compounds have the formula HO-CHa-JJ-CH-CHr-OH wherein R and R are the same or different and each of R and R are alkyl groups of one to carbon atoms, preferably one to four carbon atoms. The invention compounds are useful solvents and humectants as well as intermediates in the preparation of alkyd resins and plasticizers for resinous materials such as polyvinyl chloride compositions.

The instant novel 3,3-dialkyl-l,2,4-butanetriols can be prepared according to the method of this invention by the catalytic hydrogenation of certain bicyclic furodioxoles. In general terms, the method of preparing the invention compounds comprises the catalytic hydrogenation, preferably in the presence of water, of certain bicyclic furodioxoles, hereinafter more fully described, at temperatures in the range of 75C. to 175C. at pressures ranging from about 100 to 10,000 psi. In a more preferred embodiment, the bicyclic furodioxole is preheated to the hydrogenation temperature under a hydrogen atmosphere at a pressure below the actual hydrogenation pressure. Following this preheat, the pressure is elevated to the desired level at which the reduction is effected. The product triol can be recovered by any suitable means from the crude hydrogenation effluent.

Bicyclic furodioxole compounds suitable for use in the preparation of the novel polyhydroxy compounds of this invention include tetrahydro-2-alkyl-6,6- dialkylfuro-[2,3-d]-l ,3-dioxoI-5-ols of the formula:

wherein R and R are the same or different and each of R and R are alkyl groups of one to 10 carbon atoms, preferably one to four carbon atoms. The aqueous bases which are most effective in the condensation include the alkali metal carbonates and acetates such as sodium carbonate, potassium carbonate and sodium acetate. A preferred bicyclic furodioxole is tetrahydro- 2-isopropyl-6,6-dimethylfuro-[2,3-d1-l ,3-dioxol-5-0l, which is formed from the condensation of isobutyraldehyde and glyoxal. Tetrahydro-2-isopropyl-6,6- dimethyIfuro-[2,3-d]-l,3-dioxol-5-ol is hydrogenated according to the method of our invention to yield 3,3- dimethyl-l,2,4-butanetriol as a particularly preferred embodiment of our invention.

The catalytic hydrogenation of the bicyclic furodioxole to yield the 3,3-dialkyl-l,2,4-butanetriols of the invention can be illustrated by the following equation wherein R and R are as previously described.

It will be noted that the bicyclic furodioxole compound has three carbon-oxygen bonds which must be rather specifically broken in order to obtain the desired product:

HO-CH Generally, the hydrogenolysis of aliphatic carbonoxygen ether bonds is a reaction ordinarily requiring elevated temperatures. For example, it has been reported that dialkyl ethers are stable to hydrogen at temperatures less than 250C. over nickel, [Adkins, Reaction of Hydrogen with Organic Compounds over Copper-Chromium Oxide and Nickel Catalysts, University of Wisconsin Press (1937) p. 73]. It has also been reported that the reduction of tetrahydrofurfuryl alcohol to 1,5-pentanediol was carried out at 255C. over copper chromite, [Kaufman et al., Organic Synthesis, 26 83 1946)].

However, the bicyclic furodioxole compounds are susceptible to thermal decomposition, forming hydroxyfuranones:

The hydroxyfuranones are more stable to hydrogenation and the formation of these compounds by thermal decomposition deleteriously affects the yield of desired triol.

The triol itself will undergo chain scission to further decrease the yield of desired product and further complicate separation and recovery of the product:

In order to obtain commercial yields of the triol, it would be necessary that hydrogenation of the source material be effected under conditions such that hydrogenolysis of the three carbon-oxygen ether bonds takes place with a minimum of thermal decomposition of bicyclic furodioxole to a hydroxyfuranone as well as a minimum of hydrogenolysis or chain scission of the product triol.

We have found that bicyclic furodioxoles can be converted to 3,3-dialkyl-l,2,4-butanetriols at high conversions and yields with little, if any, thermal decomposition of bicyclic furodioxole to hydroxyfuranone compounds and the substantial elimination of hydrogenolysis or chain scission of the trio]. The desired conversion is accomplished by the catalytic hydrogenation, preferably in the presence of water, of the starting bicyclic furodioxole at moderate temperatures and superatmospheric pressures. Thus, according to the process of our invention, when bicyclic furodioxole compounds are catalytically hydrogenated at a temperature in the range of about 75C. to about 175C., preferably about 120C. to about 150C., 3,3-dia1kyl-1,2,4-butanetriols can be produced in high conversions and yields with minimum undesirable side effects. The hydrogenation is effected at pressures ranging from about 100 psi to about 10,000 psi, preferably about 100 psi to about 6,000 psi, with excellent results being obtained at pressures in the range of 2,000-5,000 psi. It has also been found beneficial to preheat or soak the starting material in the presence of the catalyst for from about 30 minutes to about 4 hours under a hydrogen atmosphere at a pressure below the actual hydrogenation pressure,v for example, from about 100 to about 1,500 psi. After the preheat period, the pressure is raised to the desired level, say on the order of 2,000 to 6,000 psi, at which reduction is effected. In a particularly preferred embodiment, the starting material isplaced in contact with the catalyst under a hydrogen atmosphere at a pressure in the range of about 100 psi to about 1,500 psi, more particularly, 1,000 to 1,500 psi. The temperature is raised to the hydrogenation temperature, e.g., 75C. to 175C., and the pressure is then raised to the desired level, e.g., 2,000-6,000 psi, at which reduction is effected.

The catalysts useful in the process of our invention include the hydrogenation catalysts, e.g., metals of Groups V-B, VI-B, VII-B and VIII of the periodic system and compounds thereof. Conventional mixed hydrogenation catalysts such as copper-chromium oxide catalysts, may also be used. Representative catalysts include rhdoium, ruthenium, rhenium, osmium, iridium, palladium, platinum, copper-chromium oxide (copper chromite), iron, copper, nickel and cobalt. The metals may be used in the form of Raney catalysts. The catalysts can be used in finely divided or pelleted form as such or can be supported on an inert carrier such as silica, alumina, silica gel, pumice, kielseguhr, etc. Preferred catalysts include Raney nickel, cobalt, palladium on alumina, and copper chromite. The concentration of the catalyst is not critical and will generally be in the range of about 0.5 to about 20 weight percent, preferably 0.5 to 12 weight percent, based on furodioxole charge.

The presence of water is advantageous in achieving maximum catalytic efficiency. With water present, catalyst concentrations as low as 0.5 to 2.0 weight percent, based on furodioxole charged, can be used to obtain the product trio] in high conversions and yields. The concentration of water is not critical and can be varied from 20 to percent of the furodioxole charged. Higher concentrations of water may be used although there appears to be no advantage in doing so. If desired, the use of water can be completely eliminated by using a sufficiently high catalyst concentration, e.g., 10 percent, based on the furodioxole charged.

The following examples are set forth for purposes of illustrating the invention. EXAMPLE 1 Preparation of the bicyclic furodioxole, Tetrahydro-2- isopropy1-6,6-dimethylfuro-[2,3-d]-1,3-dioxo1-5-ol.

A solution of 450 g. of potassium carbonate dissolved in 450 g. of water is added incrementally to a stirred mixture consisting of 6,000 ml. ofwater, 1800 g. of isobutyraldehyde and 1,800 g. of glyoxal. The time required for addition is 2 hours. During the addition, the reaction temperature increases from 24C. to 42C. After addition is complete, the mixture is stirred for 4 additional hours. An organic layer is separated from to reaction mixture. The crude product is washed once with an equal volume of water and then is heated to 50C. at reduced pressures to remove water and unreacted aldehydes. The resulting base product solidifies to give a white waxy solid. Tetrahydro-2-isopropy1-6,6- dimethylfuro-[2,3-d]-l,3-dioxol'5-ol (2,020 g.) is obtained.

EXAMPLE 2 Preparation of 3,3-Dimethyl-l ,2,4-Butanetrio1 A mixture consisting of 1,000 g. (4.95 moles) of tetrahydro-2-isopropyl-6,6-dimethylfuro- [2,3-d ]-l ,3- dioxol-S-ol, 1,000 g. of water and 6.25 g. of Raney nickel catalyst is charged to a 4 1. stirred autoclave. After purging with hydrogen, the mixture is heated to 100C. under a hydrogen pressure of 1,000 psi. The hydrogen pressure is then raised to 3,000 psi and the reduction is carried out at 3,000 psi and 100C. for 4 hours. After cooling, the catalyst is removed by filtration. The filtrate is distilied at reduced pressure to remove water and isobutanol. The residue is flash distilled at 2 mm. to give 650 g. (98 percent conversion) of 3,3-dimethyl- 1,2,4-butanetriol, b.p., 121-130C. at 2 mm. EXAMPLE 3 Preparation of 3,3-Dimethyl- 1 ,2,4-Butanetriol.

One mole (202 g.) of tetrahydro-2-isopropy1-6,6- dimethylfuro-[2,3-d]-l,3-dioxol-5-ol and 20 grams of Raney nickel are charged to a stirred autoclave. The mixture is heated with stirring to C. under a hydrogen atmosphere at 1,000 psi. The pressure is then alyst concentration on product conversions:

Analysis Theory Found Molecular Weight 134 134 Elemental Analysis Percent Carbon 53.73 53.89 Percent Hydrogen 10.44 10.26 Percent Hydroxyl 38.0 36.5

NMR Analysis Consistent with proposed structure Consistent with proposed SU'UCIUIC Infrared Analysis EXAMPLE 4 A series of runs is made to compare the effects of reaction temperature, time, water concentration and cat- Percent con- Water Catalyst version to concenconcen- Pres- 3,3-dimethyltration, tratiou, Temp, sure, Time, 1,2,4-butane- Run percent I percent I C. p.51 hrs triol Based on weight of lurodioxole charged.

Although the invention has been described in detail with particular reference to preferred embodiments thereof, it will be understood that variations and modifications can be effected within the spirit of the invention.

We claim:

1. A process for the preparation of a compound having the formula wherein R and R are the same or different and each of R and R is an alkyl group having from one to 10 carbon atoms, which comprises contacting a bicyclic furodioxole having the formula d 3. A process according to claim 1 wherein said hydrogenation catalyst is selected from the class consisting of palladium, platinum, ruthenium, rhenium, rhodium, nickel, cobalt, iron, copper-chromite or mixtures thereof.

4. A process according to claim 1 wherein said hydrogenation is effected at a temperature in the range of about 120C. to about 150C. and a pressure in the range of about 100 psi to about 6,000 psi.

5. A process according to claim 4 wherein said hydrogenation is effected at a pressure in the range of about 2,000 to about 6,000 psi.

6. A process according to claim 4 wherein said hydrogenation catalyst is Raney nickel.

7. A process according to claim 1 wherein said bicyclic furodioxole is contacted with hydrogen in the presence of said hydrogenation catalyst and at least 20 weight percent, based on furodioxole charged, of water.

8. A process according to claim 7 wherein said bydrogenation catalyst is selected from the group consisting of palladium, platinum, ruthenium, rhenium, rhodium, nickel, cobalt, iron, copper chromite or mixtures thereof.

9. A process according to claim 8 wherein said hydrogenation is effected at a temperature in the range of about 120C. to about 150C. and a pressure in the range of about 100 psi to about 6,000 psi.

10. A process according to claim 9 wherein said hydrogenation is effected at a pressure in the range of about 2,000 to about 6,000 psi.

11. A process according to claim 10 wherein said hydrogenation catalyst is Raney nickel.

12. A process according to claim 1 wherein said bicyclic furodioxole and said hydrogenation catalyst are preheated prior to hydrogenation at a temperature in the range of about C. to about 175C. under a hydrogen pressure in the range of to 1,500 psi and are subsequently hydrogenated at a pressure in the range of 2,000 to 10,000 psi.

13. A process according to claim 12 wherein said catalyst is selected from the class consisting of palladium, platinum, ruthenium, rhenium, rhodium, nickel, cobalt, iron, copper chromite or mixtures thereof.

14. A process according to claim 13 wherein said preheating is effected under a hydrogen pressure in the range of 1,000 to 1,500 psi.

15. A process according to claim 14 wherein said hydrogenation is effected at a pressure in the range of 2,000 to 6,000 psi.

16. A process according to claim 15 wherein said preheating is at a temperature in the range of C. to C. and said hydrogenation is effected at a temperature in the range of 120C. to 150C.

17. A process according to claim 16 wherein said hydrogenation catalyst is Raney nickel.

18. A process according to claim 1 wherein said bicyclic furodioxole, said hydrogenation catalyst and at least 20 weight percent, based on furodioxole charged, of water are preheated prior to hydrogenation at a temperature in the range of about 75C. to about C. under a hydrogen pressure in the range of about 100 to about 1,500 psi and subsequently hydrogenated at a pressure in the range of 2,000 to 10,000 psi.

19. A process according to claim 18 wherein said catalyst is selected from the class consisting of palladium,

platinum, ruthenium, rhenium, rhodium, nickel, cobalt,

iron, copper chromite or mixtures thereof.

20. A process according to claim 19 wherein said preheating is effected under a hydrogen pressure in the range of 1,000 to 1,500 psi.

21. A process according to claim 20 wherein said hydrogenation is effected at a pressure in the range of 2,000 to 6,000 psi.

22. A process according to claim 21 wherein said preheating is at a temperature in the range of 120C. to 150C. and said hydrogenation is eflected at a temperature in the range of 120C. to 150C.

23. A process according to claim 22 wherein said hydrogenation catalyst is Raney nickel.

24. A process according to claim 3 for preparing 3,3- dimethyl-1,2,4-butanetriol wherein said bicyclic furodioxole is tetrahydro-Z-isopropyl-6,6- dimethylfuro-[ 2,3-d]-1 ,3-dioxol--ol. 

2. A process in accordance with claim 2 wherein each of R1 and R2 is an alkyl group having from one to four carbon atoms.
 3. A process according to claim 1 wherein said hydrogenation catalyst is selected from the class consisting of palladium, platinum, ruthenium, rhenium, rhodium, nickel, cobalt, iron, copper-chromite or mixtures thereof.
 4. A process according to claim 1 wherein said hydrogenation is effected at a temperature in the range of about 120*C. to about 150*C. and a pressure in the range of about 100 psi to about 6, 000 psi.
 5. A process according to claim 4 wherein said hydrogenation is effected at a pressure in the range of about 2,000 to about 6,000 psi.
 6. A process According to claim 4 wherein said hydrogenation catalyst is Raney nickel.
 7. A process according to claim 1 wherein said bicyclic furodioxole is contacted with hydrogen in the presence of said hydrogenation catalyst and at least 20 weight percent, based on furodioxole charged, of water.
 8. A process according to claim 7 wherein said hydrogenation catalyst is selected from the group consisting of palladium, platinum, ruthenium, rhenium, rhodium, nickel, cobalt, iron, copper chromite or mixtures thereof.
 9. A process according to claim 8 wherein said hydrogenation is effected at a temperature in the range of about 120*C. to about 150*C. and a pressure in the range of about 100 psi to about 6, 000 psi.
 10. A process according to claim 9 wherein said hydrogenation is effected at a pressure in the range of about 2,000 to about 6,000 psi.
 11. A process according to claim 10 wherein said hydrogenation catalyst is Raney nickel.
 12. A process according to claim 1 wherein said bicyclic furodioxole and said hydrogenation catalyst are preheated prior to hydrogenation at a temperature in the range of about 75*C. to about 175*C. under a hydrogen pressure in the range of 100 to 1, 500 psi and are subsequently hydrogenated at a pressure in the range of 2,000 to 10,000 psi.
 13. A process according to claim 12 wherein said catalyst is selected from the class consisting of palladium, platinum, ruthenium, rhenium, rhodium, nickel, cobalt, iron, copper chromite or mixtures thereof.
 14. A process according to claim 13 wherein said preheating is effected under a hydrogen pressure in the range of 1,000 to 1,500 psi.
 15. A process according to claim 14 wherein said hydrogenation is effected at a pressure in the range of 2,000 to 6,000 psi.
 16. A process according to claim 15 wherein said preheating is at a temperature in the range of 120*C. to 150*C. and said hydrogenation is effected at a temperature in the range of 120*C. to 150*C.
 17. A process according to claim 16 wherein said hydrogenation catalyst is Raney nickel.
 18. A process according to claim 1 wherein said bicyclic furodioxole, said hydrogenation catalyst and at least 20 weight percent, based on furodioxole charged, of water are preheated prior to hydrogenation at a temperature in the range of about 75*C. to about 175*C. under a hydrogen pressure in the range of about 100 to about 1,500 psi and subsequently hydrogenated at a pressure in the range of 2,000 to 10,000 psi.
 19. A process according to claim 18 wherein said catalyst is selected from the class consisting of palladium, platinum, ruthenium, rhenium, rhodium, nickel, cobalt, iron, copper chromite or mixtures thereof.
 20. A process according to claim 19 wherein said preheating is effected under a hydrogen pressure in the range of 1,000 to 1,500 psi.
 21. A process according to claim 20 wherein said hydrogenation is effected at a pressure in the range of 2,000 to 6,000 psi.
 22. A process according to claim 21 wherein said preheating is at a temperature in the range of 120*C. to 150*C. and said hydrogenation is effected at a temperature in the range of 120*C. to 150*C.
 23. A process according to claim 22 wherein said hydrogenation catalyst is Raney nickel.
 24. A process according to claim 3 for preparing 3,3-dimethyl-1, 2,4-butanetriol wherein said bicyclic furodioxole is tetrahydro-2-isopropyl-6,6-dimethylfuro-(2,3-d)-1,3-dioxol-5-ol.
 25. A process according to claim 8 for preparing 3,3-dimethyl-1, 2,4-butanetriol wherein said bicyclic furodioxole is tetrahydro-2-isopropyl-6,6-dimethylfuro-(2,3-d)-1,3-dioxol-5-ol.
 26. A process according to claim 13 for Preparing 3,3-dimethyl-1,2,4-butanetriol wherein said bicyclic furodioxole is tetrahydro-2-isopropyl-6,6-dimethylfuro-(2,3-d)-1,3-dioxol-5-ol.
 27. A process according to claim 19 for preparing 3,3-dimethyl-1,2,4-butanetriol wherein said bicyclic furodioxole is tetrahydro-2-isopropyl-6,6-dimethylfuro-(2,3-d)-1,3-dioxol-5-ol.
 28. A process according to claim 23 for preparing 3,3-dimethyl-1,2,4-butanetriol wherein said bicyclic furodioxole is tetrahydro-2-isopropyl-6,6-dimethylfuro-(2,3-d)-1,3-dioxol-5-ol. 